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WO2005093909A1 - Planar connector - Google Patents

Planar connector Download PDF

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Publication number
WO2005093909A1
WO2005093909A1 PCT/JP2005/006220 JP2005006220W WO2005093909A1 WO 2005093909 A1 WO2005093909 A1 WO 2005093909A1 JP 2005006220 W JP2005006220 W JP 2005006220W WO 2005093909 A1 WO2005093909 A1 WO 2005093909A1
Authority
WO
WIPO (PCT)
Prior art keywords
less
fibrous filler
resin composition
composite resin
connector
Prior art date
Application number
PCT/JP2005/006220
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroki Fukatsu
Kazufumi Watanabe
Toshio Shiwaku
Hirokazu Oshiba
Original Assignee
Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Priority to US10/592,362 priority Critical patent/US7789670B2/en
Publication of WO2005093909A1 publication Critical patent/WO2005093909A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/12Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/12Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity

Definitions

  • the present invention relates to a planar connector having a lattice structure inside an outer frame such as a CPU socket.
  • Liquid crystalline polymer is known as a material that has excellent dimensional accuracy, vibration damping properties, and fluidity among thermoplastic resins and has extremely low burr generation during molding.
  • liquid crystalline polymers have been widely used as materials for various electronic components.
  • a liquid crystalline polymer composition reinforced with glass fiber has been adopted as a connector.
  • the pitch interval of the grid part required in recent years is 2 or less, and the thickness of the resin part of the grid part holding the terminal
  • its performance was insufficient for use as a very thin flat connector with a thickness of less than 0.5 sq.m. That is, in such a very thin planar connector having a lattice portion, if the lattice portion is to be filled with resin, the fluidity is not sufficient. Therefore, there is a problem in that the filling pressure is increased, and the resulting warpage of the flat connector is increased.
  • liquid crystalline polymer composition with good flowability with a small amount of glass fiber added.However, such a composition results in insufficient strength and reflow during mounting. This causes a problem of deformation.
  • the pitch of the lattice portion is 2 mm or less, and the thickness of the lattice portion is 0 mm.
  • the pitch of the lattice portion is 2 mm or less, and the thickness of the lattice portion is 0 mm.
  • the present inventors have conducted intensive searches and studies to provide a liquid crystal polymer planar connector having an excellent balance of performance, and found that the fibrous compound to be blended in the fiber reinforced liquid crystal polymer composition was When the weight average length of the filler and the amount of the filler are in a certain relationship, it was found that a flat connector having good moldability and excellent in all properties such as flatness, warpage and heat resistance was obtained.
  • the present invention has been completed.
  • the present invention provides (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a composite resin composition (provided that (B) the amount of the fibrous filler and the weight average length thereof are The relationship is a planar connector having a lattice structure inside the outer frame, which is formed from the following area (D that satisfies the definition of the area (D)).
  • the X-axis is calculated based on (B) the amount of the fibrous filler ((C)% by weight in the composite resin composition), The area surrounded by the following functions (1) to (5), where the Y axis is (B) the weight average length of the fibrous filler ( ⁇ ⁇ ⁇ )
  • the present invention is also an application of the (C) flat connector having a lattice structure inside the outer frame of the composite resin composition.
  • FIG. 1 is a view showing a region which is a relationship between a blending amount of a fibrous filler and a weight average length in a composite resin composition specified in the present invention.
  • FIGS. 2A and 2B are diagrams showing a planar connector 1 formed in the embodiment, where FIG. 2A is a plan view, FIG. 2B is a right side view, FIG. 2C is a front view, and FIG. (E) is a diagram showing the details of part B.
  • the unit of the numerical value in the figure is the thigh.
  • FIG. 3 is a diagram schematically showing the screw of the extruder used in the example.
  • the liquid crystalline polymer (A) used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic molten phase.
  • the properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing the molten sample placed on the Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere.
  • a liquid crystalline polymer applicable to the present invention is inspected between orthogonal polarizers, even if it is in a molten stationary state, polarized light is normally transmitted, and it exhibits optical anisotropy.
  • the liquid crystal polymer (A) as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyesteramide, and the aromatic polyester or the aromatic polyesteramide is partially contained in the same molecular chain. Included polyesters are also in that range. These are preferably at least about 2.0 dl / g, more preferably 2.0-1.0 dl Zg, when dissolved at a concentration of 0.1% by weight in pentafluorophenol at 60 ° C. Those having a logarithmic viscosity (I.V.) are used.
  • the aromatic polyester or aromatic polyesteramide as the liquid crystalline polymer (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. Aromatic polyesters and aromatic polyesteramides having at least one kind of compound as a constituent component. More specifically,
  • the specific compound constituting the liquid crystalline polymer (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; —Dihydroxynaphthalene, 1,4-dihydroxynaphthylene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, aromatic diols such as compounds represented by the following general formulas (I) and (II) Terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula ( ⁇ ); Aromatic dicarboxylic acids; examples thereof include aromatic amines such as P-aminophenol and P-phenylenediamine.
  • liquid crystalline polymers (A) to which the present invention is applied are aromatic polyesters containing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid as main constituent units.
  • the (C) composite resin composition used in the present invention is obtained by blending (B) a fibrous filler with the above (A) liquid crystalline polymer. It is essential that the relationship with the weight average length satisfies the requirements of the following area (D).
  • the X axis is (B) the amount of the fibrous filler (% by weight in the composite resin composition), and the Y axis is (B) the weight average length ( ⁇ m) of the fibrous filler. Area enclosed by functions (1) to (5)
  • weight average length of the fibrous filler is less than 160] II, the reinforcing effect is small, and the desired effect cannot be obtained even if the amount of the filler is increased. Also, (ii) if the weight average length of the fibrous filler exceeds 360 / _im, the fluidity will deteriorate even if the blending amount is reduced, and a connector with excellent flatness will not be obtained.
  • the term “( ⁇ ) weight average length of the fibrous filler” in the present invention is a value in a molded article, and can be measured by a method described later.
  • the fiber diameter of the fibrous filler is not particularly limited, but generally about 5 to 15 m is used. '
  • fibrous filler (B) used in the present invention examples include glass fibers, carbon fibers, whiskers, inorganic fibers, and ore fibers. Glass fibers are preferred.
  • a composition having such an apparent melt viscosity uses a liquid crystalline polymer having a general melt viscosity (10 to 100 Pa ⁇ s, preferably 10 to 40 Pa ⁇ s). It is obtained when (B) fibrous filler is blended within the range satisfying the conditions.
  • the method for obtaining such a composition is not particularly limited, but melt kneading using an extruder is generally used. However, in many cases, it cannot be obtained by the usual extrusion method in which the fibrous filler is fed from the side to the molten liquid crystalline polymer. For this reason, the liquid crystalline polymer composition containing the fibrous filler once melt-kneaded is melt-kneaded again, and the liquid crystalline polymer in the form of pellets (particle size of 1 thigh or more) is mixed with the fibrous filler from the side. It is necessary to use a feeding method or the like. Preferably, a method of feeding a pellet-like liquid crystalline polymer from the side having a small heat history is used.
  • the extruder to be used is preferably a twin-screw extruder with a side feed.
  • planar connector is a connector as shown in FIG. 2 molded in the embodiment, and it has several hundred pins in a product of about 40 thighs x 40 marauders x 1 thigh. It has a number of holes.
  • the planar connector according to the present invention may have an opening of an appropriate size in the lattice.
  • the pitch interval of the grid portion is less than 2 mm (1.2 mm), and the thickness of the resin portion of the grid portion holding the terminals is reduced. It is possible to mold very thin flat connectors with a moldability of less than 0.5 (less than 0.18 ⁇ ) and excellent flatness.
  • the flatness before going through one IR riff opening process for surface mounting at a peak temperature of 230 to 280 ° C is 0.09 or less, and If the difference between the front and rear flatness is not more than 0.02 s, it can be said that it has practically excellent flatness.
  • a molding method for obtaining a connector having such excellent flatness is not particularly limited, but an economical injection molding method is preferably used.
  • an economical injection molding method is preferably used.
  • the temperature of the cylinder of the molding machine is preferably equal to or higher than the melting point T of the liquid crystalline polymer.
  • Cylinder temperature is T ° C ⁇ (T + 30) due to problems such as nose dripping from the cylinder nozzle.
  • C preferably T ⁇ (T + 15).
  • the mold temperature is preferably from 70 to 100 ° C.
  • the molding is preferably performed at 150 mm / sec or more. If the injection speed is low, only unfilled molded products can be obtained, or even if a completely filled molded product is obtained, the molding pressure will be high and the residual internal stress will be large, and only connectors with poor flatness will be obtained. May not be possible.
  • Additives such as nucleating agent, pigment such as bonbon black, inorganic calcined pigment, antioxidant, stabilizer, plasticizer, lubricant, release agent and flame retardant to the composite resin composition.
  • a composition to which desired properties are imparted by addition is also included in the range of the composite resin composition (C) referred to in the present invention.
  • the obtained connector was left standing on a horizontal desk, and the height of the connector was measured with a Mitutoyo QuickVision 404PR0CNC image measuring machine. At that time, the position of 0.5 thigh was measured at 10 thigh intervals from one end of the connector, and the difference between the maximum height and the minimum height was defined as the flatness.
  • test pieces of the liquid crystalline polymer composition containing glass fibers were prepared under the following conditions and evaluated. The results shown in Table 2 were obtained. [Manufacturing conditions]
  • Nittobo PF70 fiber diameter ( ⁇ fiber length 8 ⁇ ⁇ milled fiber) • Lubricant; Unistar manufactured by NOF Corporation ⁇ -476
  • Fig. 3 shows the outline of the screw of the extruder.
  • Plasticization section 12; C4 to C5 Composition: from the upstream, forward kneading, reverse kneading, length 128 thighs
  • Kneading part 14; C6 to C8 (Construction: from upstream, forward kneading, orthogonal kneading, reverse nipping, reverse flight, forward kneading, reverse kneading, reverse flight, length 352 thighs)
  • Screw-in type loss-in-weight feeder manufactured by Nippon Steel Works Feeder to side feed opening;
  • Cylinder temperature Only cylinder C1 at main feed port 11 was 200 ° C, and all other cylinder temperatures were 350 ° C.
  • a pellet of liquid crystalline polymer was supplied from the main feed port 11 and the side feed port 13
  • a lubricant was supplied from the main feed port 11
  • a glass fiber was supplied from the side feed port 13.
  • the side feed port was supplied using a biaxial side feeder, and the ratio of liquid crystalline polymer pellets, lubricant, and glass fiber was controlled using a weight feeder so as to be as shown in Table 1.
  • Screw-The number of revolutions and the extrusion rate are set as shown in Table 1. After the molten resin composition discharged from the die 16 in the form of a strand is conveyed by a mesh belt conveyor manufactured by Yunaka Manufacturing Co., Ltd., and cooled by spray spray ⁇ Cutting was performed to obtain pellets. The test pieces were prepared from the pellets using an injection molding machine and evaluated. The results shown in Table 2 were obtained.
  • Example 1 29.7 0.3 30 40 300 35 Example 2 9.7 0.3 50 40 300 35
  • Example 3 14.7 0.3 45 40 300 35
  • Example 4 14.7 0.3 40 45 300 25
  • Example 5 14.7 0.3 35 50 300 25
  • Comparative example 1 9.7 0.3 60
  • Comparative Example 2 64.7 0.3 ⁇ 35 300 25
  • Comparative Example 3 64.7 0.3 ⁇ 35 300 25
  • Comparative Example 4 9.7 0.3 55 35 300
  • Comparative Example 7 44.7 0.3 5 50 300 25
  • Comparative example 8 39.7 0.3 5 55 300 25
  • Example 1 40 320 40 0.073 0.009 16.2
  • Example 2 40 190 36 0.059 0.003 15.6
  • Example 3 40 226 31 0.048 0.002 15.6
  • Example 4 45 264 37 0.083 0.009 18.5
  • Example 5 50 255 39 0.083 0.007 20.0
  • Comparative example 1 30 214 32 0.061 0.045 1.4.0
  • Comparative Example 2 35 370 57 0.073 0.021 17.8
  • Comparative Example 3 35 430 59 0.069 0.027 17.9
  • Comparative Example 4 35 229 32 0.067 0.102 15.8
  • Comparative Example 5 40 397 56 0.092 0.010 19.4
  • Comparative Example 6 45 359 60 * * 20.5 Comparative Example 7 50 315 67 * * 20.9 Comparative Example 8 55 305 80 * * 22.0 Comparative Example

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Connector Housings Or Holding Contact Members (AREA)

Abstract

A planar connector having an outer frame and a lattice structure provided inside the outer frame, which comprises (C) a composite resin composition comprising (A) a liquid crystalline polymer and (B) a fibrous filler, wherein the relationship between the amount of the fibrous filler (B) and the weight average length thereof is controlled within a specific scope. The above planar connector is excellent in all of the performance capabilities such as formability, the degree of planarity, warping characteristics and heat resistance, even when it is a very thin planar connector having a pitch in the lattice portion of 2 mm or less and a thickness of the lattice portion of 0.5 mm or less.

Description

明細書 平面状コネクター 技術分野  Description Flat connector Technical field
本発明は、 CPUソケット等の外枠内部に格子構造を有する平面状コネクタ一 に関する。  The present invention relates to a planar connector having a lattice structure inside an outer frame such as a CPU socket.
背景技術 Background art
液晶性ポリマーは、 熱可塑性樹脂の中でも寸法精度、 制振性、 流動性に優れ、 成形時のバリ発生が極めて少ない材料として知られている。 従来、 このような特 徵を活かし、 液晶性ポリマーが各種電子部品の材料として多く採用されてきた。 特に、 近年のエレクトロニクス機器の高性能化に伴う、 コネクタ一の高耐熱化 (実装技術による生産性向上) 、 高密度化 (多芯化) 、 小型化という時代の要請 もあり、 上記液晶性ポリマーの特徴を活かし、 ガラス繊維で強化された液晶性ポ リマー組成物がコネクタ一として採用されている (全調査 エンジニアリングプ ラスチックス, 92—' 93」 、 182〜194頁、 1992年発行、 J P— A 9一 204951、 J P—A6— 240115) 。 CPUソケットに代表される 外枠内部に格子構造を有する平面状コネクターにおいては、 上記高耐熱化、 高密 度化、 小型化の傾向が顕著であり、 ガラス繊維で強化された液晶性ポリマー組成 物が多く採用されている。  Liquid crystalline polymer is known as a material that has excellent dimensional accuracy, vibration damping properties, and fluidity among thermoplastic resins and has extremely low burr generation during molding. In the past, taking advantage of such characteristics, liquid crystalline polymers have been widely used as materials for various electronic components. In particular, there is a demand in the age of high heat resistance of connectors (improvement of productivity by mounting technology), high density (multiple cores), and miniaturization due to recent high performance of electronic equipment. Utilizing the features of (1), a liquid crystalline polymer composition reinforced with glass fiber has been adopted as a connector. (All surveys Engineering Plastics, 92-'93, pp. 182-194, published in 1992, JP-A 9-204951, JP-A6-240115). In a flat connector having a lattice structure inside the outer frame represented by a CPU socket, the above-mentioned tendency of high heat resistance, high density, and miniaturization is remarkable, and a liquid crystal polymer composition reinforced with glass fiber is used. Many are adopted.
し力、し、 ある程度流動性の良い ラス繊維強化液晶性ポリマー組成物であって も、 近年要求されている格子部のピッチ間隔が 2匪以下、 端子を保持する格子部 の樹脂部分の肉厚が 0.5讓以下という非常に薄肉の平面状コネクタ一として使用 するには性能が不十分であった。 即ち、 このような格子部の非常に薄肉の平面状 コネクタ一においては、 格子部へ樹脂を充填しょうとすると、 流動性が十分でな いために充填圧が高くなり、 結果として得られる平面状コネクタ一のそり変形量 が多くなるという問題がある。 Even if the lath fiber reinforced liquid crystalline polymer composition has good fluidity to some extent, the pitch interval of the grid part required in recent years is 2 or less, and the thickness of the resin part of the grid part holding the terminal However, its performance was insufficient for use as a very thin flat connector with a thickness of less than 0.5 sq.m. That is, in such a very thin planar connector having a lattice portion, if the lattice portion is to be filled with resin, the fluidity is not sufficient. Therefore, there is a problem in that the filling pressure is increased, and the resulting warpage of the flat connector is increased.
この問題を解決するには、 ガラス繊維の添加量を少なくした流動性の良好な液 晶性ポリマー組成物の使用が考えられるが、 このような組成物では強度不足とな り、 実装時のリフローにより変形するという問題が生じる。  In order to solve this problem, it is conceivable to use a liquid crystalline polymer composition with good flowability with a small amount of glass fiber added.However, such a composition results in insufficient strength and reflow during mounting. This causes a problem of deformation.
このように、 未だ性能バランスの優れた液晶性ポリマー製平面状コネクタ一は 得られていないのが現状である。 発明の開示  As described above, a flat connector made of a liquid crystalline polymer with an excellent balance of performance has not yet been obtained. Disclosure of the invention
以上のように、 格子構造を有する平面状コネクターに用いる液晶性ポリマー組 成物に関しては様々な検討が行われているが、特に格子部のピッチ間隔が 2 mm以 下、 格子部の厚みが 0. 5腿以下といった非常に薄肉の平面状コネクタ一に関して は、 成形性、 平面度、 そり変形、 耐熱性等の性能の全てに優れた材料は存在しな かつ 。  As described above, various studies have been conducted on the liquid crystalline polymer composition used for the planar connector having a lattice structure, but in particular, the pitch of the lattice portion is 2 mm or less, and the thickness of the lattice portion is 0 mm. For very thin flat connectors such as those with 5 or less thighs, there is no material that is excellent in all of the properties such as moldability, flatness, warpage, and heat resistance.
本発明者等は上記問題点に鑑み、 性能バランスの優れた液晶性ポリマー製平面 状コネクターを提供すべく鋭意探索、 検討を行ったところ、 繊維強化液晶性ポリ マー組成物において、 配合する繊維状充填剤の重量平均長さと配合量が一定の関 係にある場合、 成形性良く、 平面度、 そり変形、 耐熱性等の性能の全てに優れた 平面状コネク夕一が得られることを見出し、 本発明を完成するに至つた。  In view of the above problems, the present inventors have conducted intensive searches and studies to provide a liquid crystal polymer planar connector having an excellent balance of performance, and found that the fibrous compound to be blended in the fiber reinforced liquid crystal polymer composition was When the weight average length of the filler and the amount of the filler are in a certain relationship, it was found that a flat connector having good moldability and excellent in all properties such as flatness, warpage and heat resistance was obtained. The present invention has been completed.
即ち本発明は、 (A)液晶性ポリマーに (B)繊維状充填剤を配合した (C)複合樹脂組成 物 (但し、配合する (B)繊維状充填剤の配合量と重量平均長さとの関係が、以下の領域 (D)の規定内を満足するもの)から形成される、外枠の内部に格子構造を有する平面状 コネ、クタ一である。  That is, the present invention provides (A) a liquid crystalline polymer, (B) a fibrous filler, and (C) a composite resin composition (provided that (B) the amount of the fibrous filler and the weight average length thereof are The relationship is a planar connector having a lattice structure inside the outer frame, which is formed from the following area (D that satisfies the definition of the area (D)).
[領域 (D) ]  [Area (D)]
X軸を (B) 繊維状充填剤の配合量 ((C) 複合樹脂組成物中の重量%) 、 Y軸を (B) 繊維状充填剤の重量平均長さ ( ·ίπι ) として、 以下の(1) 〜(5) の関数で囲まれる領域 The X-axis is calculated based on (B) the amount of the fibrous filler ((C)% by weight in the composite resin composition), The area surrounded by the following functions (1) to (5), where the Y axis is (B) the weight average length of the fibrous filler (· 状 πι)
(1) Χ =36  (1) Χ = 36
(2) Χ=53  (2) Χ = 53
(3) Υ = 160  (3) Υ = 160
(4) Υ=360  (4) Υ = 360
(5) Υ= (18222/Χ) -84. 44 また、 本発明は上記 (C)複合樹脂組成物の外枠の内部に格子構造を有する平面状 コネクターへの用途である。 図面の簡単な説明  (5) Υ = (18222 / Χ) -84.44 The present invention is also an application of the (C) flat connector having a lattice structure inside the outer frame of the composite resin composition. Brief Description of Drawings
図 1は本発明で規定する複合樹脂組成物における繊維状充填剤の配合量と重量 平均長さとの関係である領域を示す図である。  FIG. 1 is a view showing a region which is a relationship between a blending amount of a fibrous filler and a weight average length in a composite resin composition specified in the present invention.
図 2は実施例で成形した平面状コネクタ一を示す図であり、 (a) は平面図、 (b) は右側面図、 (c) は正面図、 (d) は A部の詳細を示す図、 (e) は B部の詳細を示 す図である。 尚、 図中の数値の単位は腿である。  FIGS. 2A and 2B are diagrams showing a planar connector 1 formed in the embodiment, where FIG. 2A is a plan view, FIG. 2B is a right side view, FIG. 2C is a front view, and FIG. (E) is a diagram showing the details of part B. The unit of the numerical value in the figure is the thigh.
図 3は実施例で使用した押出機のスクリユーの概略を示す図である。  FIG. 3 is a diagram schematically showing the screw of the extruder used in the example.
図中の符号を説明する。  The reference numerals in the figure will be described.
1…樹脂溜り '- 1… Resin pool '-
2…ピッチ間隔 2 ... Pitch interval
3…格子部の厚み  3 ... Grating thickness
11…メインフィード口  11… Main feed port
12…可塑化部 '  12 ... Plasticizing part ''
13…サイドフィード口 14…混練部 13 ... Side feed port 14 ... Kneading part
15···ベント口  15Vent port
16…ダイ  16… die
17…減圧装置 発明の詳細な説明  17 ... Decompression device Detailed description of the invention
以下、 本発明を詳細に説明する。 本発明で使用する液晶性ポリマー (A) とは、 光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。 異方性 溶融相の性質は、 直交偏光子を利用した慣用の偏光検査法により確認することが 出来る。 より具体的には、 異方性溶融相の確認は、 L e i t z偏光顕微鏡を使用 し、 L e i t zホットステージに載せた溶融試料を窒素雰囲気下で 4 0倍の倍率 で観察することにより実施できる。 本発明に適用できる液晶性ポリマ一は直交偏 光子の間で検査したときに、 たとえ溶融静止状態であつても偏光は通常透過し、 光学的に異方性を示す。  Hereinafter, the present invention will be described in detail. The liquid crystalline polymer (A) used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic molten phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing the molten sample placed on the Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere. When a liquid crystalline polymer applicable to the present invention is inspected between orthogonal polarizers, even if it is in a molten stationary state, polarized light is normally transmitted, and it exhibits optical anisotropy.
前記のような液晶性ポリマー (A) としては特に限定されないが、 芳香族ポリエ ステル又は芳香族ポリエステルアミドであることが好ましく、 芳香族ポリエステ ル又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルも その範囲にある。これらは 6 0 °Cでペン夕フルオロフェノールに濃度 0. 1重量% で溶解したときに、 好ましくは少なくとも約 2. 0 d l / g、 さらに好ましくは 2 . 0 - 1 0 . O d l Z gの対数粘度 ( I . V. ) を有するものが使用される。 本発明に適用できる液晶性ポリマー (A) としての芳香族ポリエステル又は芳香 族ポリエステルアミドとして特に好ましくは、 芳香族ヒドロキシカルボン酸、 芳 香族ヒドロキシァミン、 芳香族ジァミンの群から選ばれた少なくとも 1種以上の 化合物を構成成分として有する芳香族ポリエステル、 芳香族ポリエステルアミド である。 より具体的には、 The liquid crystal polymer (A) as described above is not particularly limited, but is preferably an aromatic polyester or an aromatic polyesteramide, and the aromatic polyester or the aromatic polyesteramide is partially contained in the same molecular chain. Included polyesters are also in that range. These are preferably at least about 2.0 dl / g, more preferably 2.0-1.0 dl Zg, when dissolved at a concentration of 0.1% by weight in pentafluorophenol at 60 ° C. Those having a logarithmic viscosity (I.V.) are used. The aromatic polyester or aromatic polyesteramide as the liquid crystalline polymer (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. Aromatic polyesters and aromatic polyesteramides having at least one kind of compound as a constituent component. More specifically,
( 1 ) 主として芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以 上からなるポリエステル;  (1) A polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof;
( 2 ) 主として (a) 芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と、 (b ) 芳香族ジカルボン酸、 脂環族ジカルボン酸およびその誘導体 の 1種又は 2種以上と、 (c ) 芳香族ジオール、 脂環族ジオール、 脂肪族ジォー ルおよびその誘導体の少なくとも 1種又は 2種以上、 とからなるポリエステル; (2) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and ( c) a polyester comprising at least one or more of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof;
( 3 ) 主として (a) 芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と、 (b ) 芳香族ヒドロキシァミン、 芳香族ジァミンおよびその誘導体 の 1種又は 2種以上と、 (c ) 芳香族ジカルボン酸、 脂環族ジカルボン酸および その誘導体の 1種又は 2種以上、 とからなるポリエステルアミド; (3) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, and (c A) a polyesteramide comprising one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof;
( 4 ) 主として (a) 芳香族ヒドロキシカルボン酸およびその誘導体の 1種又は 2種以上と、 (b ) 芳香族ヒドロキシァミン、 芳香族ジァミンおよびその誘導体 の 1種又は 2種以上と、 (c ) 芳香族ジカルボン酸、 脂環族ジカルボン酸および その誘導体の 1種又は 2種以上と、 (d) 旁香族ジオール、 脂環族ジオール、 脂 肪族ジオールおよびその誘導体の少なくとも 1種又は 2種以上、 とからなるポリ エステルアミドなどが挙げられる。 さらに上記の構成成分に必要に応じ分子量調 整剤を併用してもよい。  (4) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof, and (c) ) One or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof, and (d) at least one or two of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof As described above, there may be mentioned, for example, a polyester amide comprising Further, a molecular weight adjuster may be used in combination with the above-mentioned constituents, if necessary.
本発明に適用できる前記液晶性ポリマー (A) を構成する具体的化合物の好まし い例としては、 p—ヒドロキシ安息香酸、 6—ヒドロキシー 2—ナフトェ酸等の 芳香族ヒドロキシカルボン酸、 2 , 6—ジヒドロキシナフタレン、 1 , 4—ジヒ ドロキシナフ夕レン、 4, 4 ' ージヒドロキシビフエニル、 ハイドロキノン、 レ ゾルシン、 下記一般式 (I ) および下記一般式 (II) で表される化合物等の芳香 族ジオール;テレフタル酸、イソフタル酸、 4 , 4 ' ージフエニルジカルボン酸、 2 , 6—ナフタレンジカルボン酸および下記一般式(ΠΙ)で表される化合物等の 芳香族ジカルボン酸; P—アミノフヱノール、 P—フエ二レンジァミン等の芳香 族ァミン類が挙げられる。
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0003
Preferable examples of the specific compound constituting the liquid crystalline polymer (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; —Dihydroxynaphthalene, 1,4-dihydroxynaphthylene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, aromatic diols such as compounds represented by the following general formulas (I) and (II) Terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and compounds represented by the following general formula (ΠΙ); Aromatic dicarboxylic acids; examples thereof include aromatic amines such as P-aminophenol and P-phenylenediamine.
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0003
(但し、 X :アルキレン (C 1〜C 4 ) 、 アルキリデン、 -0- 、 -SO-、 -S02- 、 -S -、 -CO -より選ばれる基、 Y : - (CH2) n- (n = l〜4 ) 、 -0 (CH2) n0- (n = l〜4 ) より選ばれる基) (However, X: alkylene (C 1 through C 4), alkylidene, -0-, -SO-, -S0 2 - , -S -, -CO - from group selected, Y: - (CH 2) n - (n = l~4), -0 ( CH 2) n 0- (n = l~4) than group selected)
本発明が適用される特に好ましい液晶性ポリマー (A) としては、 p—ヒドロキ シ安息香酸、 6—ヒドロキシー 2—ナフトェ酸を主構成単位成分とする芳香族ポ リエステルである。  Particularly preferred liquid crystalline polymers (A) to which the present invention is applied are aromatic polyesters containing p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid as main constituent units.
本発明に使用する(C) 複合樹脂組成物は、 上記 (A) 液晶性ポリマーに (B) 繊維 状充填剤を配合したものであるが、 配合する(B) 繊維状充填剤の配合量と重量平 均長さとの関係が、 以下の領域 (D) の規定内を満足するものであることが必須で ある。  The (C) composite resin composition used in the present invention is obtained by blending (B) a fibrous filler with the above (A) liquid crystalline polymer. It is essential that the relationship with the weight average length satisfies the requirements of the following area (D).
[領域 (D) ]  [Area (D)]
X軸を (B) 繊維状充填剤の配合量 ((C) 複合樹脂組成物中の重量%) 、 Y軸を (B)繊維状充填剤の重量平均長さ (^m) として、 以下の(1) 〜(5) の関数で囲まれる領域  The X axis is (B) the amount of the fibrous filler (% by weight in the composite resin composition), and the Y axis is (B) the weight average length (^ m) of the fibrous filler. Area enclosed by functions (1) to (5)
(1) X =36  (1) X = 36
(2) X = 53 (3) Y = 160 (2) X = 53 (3) Y = 160
(4) Y=360  (4) Y = 360
(5) Υ = (18222/Χ) -84. 44 上記領域 (D) は、 図 1の Ζで示される領域であり、 基本的に (Β) 繊維状充填剤 の重量平均長さは、 (3) Y = 160 zm以上且つ(4) Υ=360 ηι以下であることが必 要である。  (5) Υ = (18222 / Χ) -84.44 The above area (D) is the area indicated by Ζ in Fig. 1. Basically, (Β) the weight average length of the fibrous filler is ( 3) It is necessary that Y = 160 zm or more and (4) Υ = 360 ηι or less.
(Β) 繊維状充填剤の重量平均長さが 160 ] II未満の場合、 補強効果が小さく、 配 合量を多くしても所望の効果を得ることができない。 また、 (Β) 繊維状充填剤の 重量平均長さが 360 /_imを超えると配合量を少なくしても流動性が悪化し、優れた 平面度のコネクタ一とはならない。 尚、' 本発明で言う(Β) 繊維状充填剤の重量平 均長さとは、 成形品中の値であり、 後記する手法により測定できる。 また、 (Β) 繊維状充填剤の繊維径は特に制限されないが、 一般的に 5〜15 ^m程度のものが 使用される。 '  (Ii) If the weight average length of the fibrous filler is less than 160] II, the reinforcing effect is small, and the desired effect cannot be obtained even if the amount of the filler is increased. Also, (ii) if the weight average length of the fibrous filler exceeds 360 / _im, the fluidity will deteriorate even if the blending amount is reduced, and a connector with excellent flatness will not be obtained. The term “(Β) weight average length of the fibrous filler” in the present invention is a value in a molded article, and can be measured by a method described later. (Ii) The fiber diameter of the fibrous filler is not particularly limited, but generally about 5 to 15 m is used. '
また、 (B) 繊維状充填剤の配合量 ((C) ネ合樹脂組成物中の配合比率) に関し ては、(1) X=36重量%以上且つ(2) X=53重量%以下であることが必要である。  Regarding (B) the blending amount of the fibrous filler ((C) the blending ratio in the resin composition), (1) X = 36% by weight or more and (2) X = 53% by weight or less. It is necessary to be.
(B) 繊維状充填剤の配合量が 36重量%枣満では、 比較的重量平均長さの長い繊 維状充填剤を用いても補強効果が小さく、 所望の効果を得ることができない。 ま た、 (B)繊維状充填剤の配合量が 53重量%を超えると比較的重量平均長さの短い 繊維状充填剤を用いても流動性が悪化し、 優れた平面度のコネクターとはならな い。  (B) When the amount of the fibrous filler is less than 36% by weight, the reinforcing effect is small even if a fibrous filler having a relatively long weight average length is used, and the desired effect cannot be obtained. In addition, when the blending amount of the fibrous filler (B) exceeds 53% by weight, even if a fibrous filler having a relatively short weight average length is used, the fluidity is deteriorated, and a connector having excellent flatness is considered. No.
更に、 上記領域 (D) は、 (5) Y= (18222/X) 一 84. 44の要件を満たす必要が ある。 即ち、 上記(1) 〜(4) の関数で囲まれる領域であっても、 (Β) 繊維状充填 剤の配合量が増える (41重量%以上) に従い、 (Β)繊維状充填剤の重量平均長さ がの短いものを使用しなければ、 流動性と強度,平面度のバランスが悪くなり、 本発明の所期の効果が得られなくなる。 Further, the area (D) must satisfy the requirement of (5) Y = (18222 / X) -84.44. That is, even in a region surrounded by the functions (1) to (4), (に 従 い) the weight of the fibrous filler increases as the blending amount of the fibrous filler increases (41% by weight or more). If the average length is not short, the balance between fluidity, strength and flatness will be poor. The desired effect of the present invention cannot be obtained.
本発明に使用する(B) 繊維状充填剤としては、 ガラス繊維、 カーボン繊維、 ゥ イスカー、 無機系繊維、 鉱石系繊維等が挙げられるが、 ガラス繊維が好ましい。 本発明に使用する(C) 複合樹脂組成物は、 流動性に優れていることが必要であ り、 これを粘度の面から規定すると、 L = 20匪、 d = Ι ΐΜのキヤピラリー式レオ メータを使用し、 温度 360°C、 剪断速度 1000// 3で1 3 0 1 1 4 4 3に準拠して 測定した見掛け溶融粘度が 55 P a · s以下のものであること力 S好ましい。 Examples of the fibrous filler (B) used in the present invention include glass fibers, carbon fibers, whiskers, inorganic fibers, and ore fibers. Glass fibers are preferred. The composite resin composition (C) used in the present invention needs to have excellent fluidity. If this is defined in terms of viscosity, a capillary rheometer with L = 20 bandages and d = ΐΜ ΐΜ using a temperature 360 ° C, at a shear rate of 1000 / / 3 1 3 0 1 1 4 4 apparent melt viscosity measured according to 3 that force S preferably of the following 55 P a · s.
このような見掛け溶融粘度を有する組成物は、 一般的な溶融粘度の液晶性ポリ マ一 (10〜100 P a · s、 好ましくは 10〜40 P a · s ) を使用し、 これに前記条 件を満たす範囲で (B) 繊維状充填剤を配合した場合に得られる。  A composition having such an apparent melt viscosity uses a liquid crystalline polymer having a general melt viscosity (10 to 100 Pa · s, preferably 10 to 40 Pa · s). It is obtained when (B) fibrous filler is blended within the range satisfying the conditions.
このような組成物を得る方法としては、 特に制限はないが、 押出機による溶融 混練が一般的に用いられる。 但し、 溶融した液晶性ポリマーにサイドから繊維状 充填剤をフィードするという通常の押出方法では得られない場合が多い。 そのた め、 一回溶融混練した繊維状充填剤配合液晶性ポリマー組成物を再度溶融混練す る方法、 サイドから繊維状充填剤と共にペレット状 (粒径 1腿以上) の液晶性ポ リマ一をフィードする方法等を用いる必要がある。 好ましくは、 熱履歴の少ない サイドからペレット状の液晶性ポリマーをフィードする方法である。 また、 使用 する押出機もサイドフィードしゃすい二軸押出機が好ましい。  The method for obtaining such a composition is not particularly limited, but melt kneading using an extruder is generally used. However, in many cases, it cannot be obtained by the usual extrusion method in which the fibrous filler is fed from the side to the molten liquid crystalline polymer. For this reason, the liquid crystalline polymer composition containing the fibrous filler once melt-kneaded is melt-kneaded again, and the liquid crystalline polymer in the form of pellets (particle size of 1 thigh or more) is mixed with the fibrous filler from the side. It is necessary to use a feeding method or the like. Preferably, a method of feeding a pellet-like liquid crystalline polymer from the side having a small heat history is used. The extruder to be used is preferably a twin-screw extruder with a side feed.
本発明の (C) 複合樹脂組成物を成形することにより、 各種平面状コネクタ一を 得ることができるが、従来、工業的に実用性のあるものが提供されていなかった、 格子部のピッチ間隔が 2腿以下、 端子を保持する格子部の樹脂部分の肉厚が 0. 5 應以下、製品全体の高さが 5. 0腿以下という非常に薄肉の平面状コネクターに特 に有効である。  By molding the (C) composite resin composition of the present invention, various planar connectors can be obtained.However, conventionally, there is no industrially practical connector. This is especially effective for very thin flat connectors, where the thickness of the resin part of the grid that holds the terminals is 0.5 mm or less and the height of the entire product is 5.0 mm or less.
このような平面状コネクターをより詳細に説明するならば、 実施例で成形した 図 2に示すようなコネクターであり、 40腿 X40匪 X 1腿程度の製品中に数百のピ ン孔数を有するものである。 図 2に示すように、 本発明で言う平面状コネクター は、 格子部の中に適当な大きさの開口部を有していても良いのは勿論である。 本発明の(C) 複合樹脂組成物を用いることにより、 図 2に示すように、 格子部 のピッチ間隔が 2顧以下(1. 2mm)、端子を保持する格子部の樹脂部分の肉厚が 0. 5廳以下 (0. 18删) という非常に薄肉の平面状コネクターを成形性良く成形する ことが可能であり、 その平面度も優れている。 To explain such a planar connector in more detail, it is a connector as shown in FIG. 2 molded in the embodiment, and it has several hundred pins in a product of about 40 thighs x 40 marauders x 1 thigh. It has a number of holes. As shown in FIG. 2, the planar connector according to the present invention may have an opening of an appropriate size in the lattice. By using the composite resin composition (C) of the present invention, as shown in FIG. 2, the pitch interval of the grid portion is less than 2 mm (1.2 mm), and the thickness of the resin portion of the grid portion holding the terminals is reduced. It is possible to mold very thin flat connectors with a moldability of less than 0.5 (less than 0.18 以下) and excellent flatness.
この平面度を数値的に規定するならば、 ピーク温度 230〜280°Cで表面実装のた めの I Rリフ口一工程を経る前の平面度が 0. 09腿以下であり、なおかつリフ口一 前後の平面度の差が 0. 02讓以下であるものは、実用上優れた平面度を有するもの と言える。  If this flatness is specified numerically, the flatness before going through one IR riff opening process for surface mounting at a peak temperature of 230 to 280 ° C is 0.09 or less, and If the difference between the front and rear flatness is not more than 0.02 s, it can be said that it has practically excellent flatness.
このような優れた平面度を有するコネクターを得る成形方法としては、 特に制 限はないが、 経済的な射出成形方法が好ましく用いられる。 射出成形でこのよう な優れた平面度を有するコネクターを得るためには、 前記の液晶性ポリマー組成 物を用いることが重要であるが、 残留内部応力のない成形条件を選ぶことが好ま しい。充填圧を低くし、得られるコネクターの残留内部応力を低下させるために、 成形機のシリンダ一温度は、 液晶性ポリマーの融点 T 以上の温度が好ましく、 またシリンダー温度が高すぎると樹脂の分解等に伴うシリンダーノズルからの鼻 タレ等の問題が発生するため、 シリンダー温度は T°C〜 (T + 3 0 ) 。C、 好まし くは T 〜(T + 1 5 ) である。また、金型温度は 7 0〜1 0 0 °Cが好ましい。 金型温度が低いと充填樹脂組成物が流動不良を起こし好ましくなく、 金型温度が 高すぎると、 バリ発生等の問題が生じ好ましくない。 射出速度については、 150m m/sec以上で成形することが好ましい。 射出速度が低いと、 未充填成形品しか得 られない場合や、 たとえ完全に充填した成形品が得られたとしても充填圧が高く 残留内部応力の大きい成形品となり、 平面度の悪いコネクターしか得られない場 合がある。 なお、 (C) 複合樹脂組成物に対し、 核剤、 力一ボンブラック、 無機焼成顔料等 の顔料、 酸化防止剤、 安定剤、 可塑剤、 滑剤、 離型剤および難燃剤等の添加剤を 添加して、 所望の特性を付与した組成物も本発明で言う(C) 複合樹脂組成物の範 囲に含まれる。 実施例 A molding method for obtaining a connector having such excellent flatness is not particularly limited, but an economical injection molding method is preferably used. In order to obtain a connector having such excellent flatness by injection molding, it is important to use the above-mentioned liquid crystalline polymer composition, but it is preferable to select molding conditions free of residual internal stress. In order to lower the filling pressure and reduce the residual internal stress of the resulting connector, the temperature of the cylinder of the molding machine is preferably equal to or higher than the melting point T of the liquid crystalline polymer. Cylinder temperature is T ° C ~ (T + 30) due to problems such as nose dripping from the cylinder nozzle. C, preferably T ~ (T + 15). The mold temperature is preferably from 70 to 100 ° C. If the mold temperature is low, the filled resin composition causes poor flow, which is not preferable. If the mold temperature is too high, problems such as burrs are generated, which is not preferable. As for the injection speed, the molding is preferably performed at 150 mm / sec or more. If the injection speed is low, only unfilled molded products can be obtained, or even if a completely filled molded product is obtained, the molding pressure will be high and the residual internal stress will be large, and only connectors with poor flatness will be obtained. May not be possible. (C) Additives such as nucleating agent, pigment such as bonbon black, inorganic calcined pigment, antioxidant, stabilizer, plasticizer, lubricant, release agent and flame retardant to the composite resin composition. A composition to which desired properties are imparted by addition is also included in the range of the composite resin composition (C) referred to in the present invention. Example
以下、 実施例により本発明を具体的に説明するが、 本発明はこれらに限定され るものではない。 尚、 実施例中の物性の測定および試験は次の方法で行った。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In addition, the measurement and the test of the physical property in an Example were performed by the following method.
(1) ガラス繊維の重量平均長さの測定 (1) Measurement of weight average length of glass fiber
樹脂組成物ペレット 5 gを 600°Cで 2時間加熱し 灰化した。 灰化残渣を 5 % ポリエチレングリコール水溶液に十分分散させた後、スポイトでシャーレに移し、 顕微鏡でガラス繊維を観察した。 同時に画像解析装置 ( (株) 二レコ製 LUZEX F S) を用いてガラス繊維  5 g of the resin composition pellets were heated at 600 ° C. for 2 hours and incinerated. After the ash residue was sufficiently dispersed in a 5% polyethylene glycol aqueous solution, it was transferred to a petri dish with a dropper, and the glass fibers were observed with a microscope. At the same time, using an image analyzer (LUZEX FS manufactured by NIRECO Co., Ltd.)
の重量平均長さを測定した。 尚、 画像解析の際には、 重なり合った繊維を別々の 繊維に分離し、 それぞれの長さを求めるよ 5なサブルーチンを適用した。 '尚、 50 m以下のガラス繊維は除外して測定している。 Was measured for weight average length. At the time of image analysis, the overlapping fibers were separated into separate fibers, and five subroutines for calculating the length of each were applied. 'Furthermore, the measurement excludes glass fibers of 50 m or less.
(2) 見掛け溶融粘度 _  (2) Apparent melt viscosity _
L = 20腿、 d = 1腿のキヤビラリ一式レオメータ ( (株) 東洋精機製キヤピロ グラフ 1 B型) を使用し、 温度 360で、 剪断速度 lOOOZ sで I S O 1 1 4 4 3に 準拠して、 見掛け溶融粘度を測定した。  L = 20 t, d = 1 thigh, using a complete set of rheometers (Capillograph 1B, manufactured by Toyo Seiki Co., Ltd.) at a temperature of 360 and a shear rate of lOOOOZs in accordance with ISO 11443, The apparent melt viscosity was measured.
(3) コネクター平面度の測定  (3) Measurement of connector flatness
樹脂組成物ペレットから、 下記成形条件で、 図 2に示すような、 全体の大きさ 39. 82匪 X 36. 82腿 X 1匪 t、 中央部に 19. 02腿 X 19. 02腿の孔開きを有し、 格子部 ピッチ間隔 1. 2匪の平面状コネクタ一 (ピン孔数 494ピン) を射出成形した。 尚、 ゲ一トは樹脂溜り反対面からのフィルムゲートを用い、 ゲート厚みは 3腿 とした。 From the resin composition pellets, under the following molding conditions, the overall size as shown in Figure 2 39.82 marauds X 36.82 thighs X 1 marauder t, 19.02 thighs x 19.02 thigh holes in the center A grid connector with a gap and a pitch interval of 1.2 was molded by injection molding with a flat connector (number of pin holes: 494 pins). The gate uses a film gate from the opposite side of the resin pool, and the gate thickness is three And
得られたコネクタ一を水平な机の上に静置し、 コネクターの高さをミツトヨ製 クイックビジョン 404PR0CNC画像測定機により測定した。 その際、 コネクタ一端 面より、 0. 5腿の位置を 10腿間隔で測定し、 最大高さと最小高さの差を平面度と した。  The obtained connector was left standing on a horizontal desk, and the height of the connector was measured with a Mitutoyo QuickVision 404PR0CNC image measuring machine. At that time, the position of 0.5 thigh was measured at 10 thigh intervals from one end of the connector, and the difference between the maximum height and the minimum height was defined as the flatness.
更に、 日本パルス技術研究所製大型卓上リフローハンダ付け装置 RF- 300を使用 し、 ピーク温度 250° (:、 加熱時間 5分の条件で加熱した後、 上述の方法で平面度 を測定し、 リフロー前後の平面度の差を求めた。  Furthermore, using a large tabletop reflow soldering device RF-300 manufactured by Nippon Pulse Research Institute, peak temperature of 250 ° (Heating time: 5 minutes) After heating, measure flatness by the above method and reflow. The difference between the front and rear flatness was determined.
[成形条件]  [Molding condition]
成形機; FANUC Q!-50C (中径ロングノズル使用) Molding machine; FANUC Q! -50C (using medium long nozzle)
シリンダー温度; 350°C— 350°C _34(TC— 330°C Cylinder temperature; 350 ° C—350 ° C_34 (TC—330 ° C
(ノズル)  (Nozzle)
金型温度; 80°C Mold temperature: 80 ° C
射出速度; 200腿/ sec Injection speed; 200 t / sec
保圧力; 29MPa Holding pressure: 29MPa
充填時間; 0. 08sec Filling time: 0.08sec
保圧時間; 1 sec Holding time: 1 sec
冷却時間; 5 sec Cooling time: 5 sec
スクリュー回転数; 120rpm Screw rotation speed; 120rpm
スクリュー背圧; 0. 5MPa Screw back pressure; 0.5MPa
(4) 曲げ弾性率 (4) Flexural modulus
125腿 X 12. 7匪 X0. 8匪の射出成形片を使用し、 ASTM D790に準拠し測定した。 実施例 1〜 5および比較例 1〜 9  125 thigh X 12.7 marauder X 0.8 We used an injection molded piece of marauder and measured according to ASTM D790. Examples 1 to 5 and Comparative Examples 1 to 9
下記条件にて、ガラス繊維を含む液晶性ポリマー組成物の上記試験片を作製し、 評価したところ、 表 2に示す結果を得た。 [製造条件] The test pieces of the liquid crystalline polymer composition containing glass fibers were prepared under the following conditions and evaluated. The results shown in Table 2 were obtained. [Manufacturing conditions]
(使用成分)  (Use ingredients)
'ポリマー;液晶性ポリマーペレット (ポリプラスチックス (株) 製、 ベクトラ 'Polymer: Liquid crystalline polymer pellet (Vectra, manufactured by Polyplastics Co., Ltd.)
E 9 5 0 i ) 、 融点 335°C、 粘度 30 P a · sのベースポリマー (350°C、 剪断速度 lOOOZ sで測定) 、 ペレツト寸法:約 5〜3腿 X約 3〜2匪 X約 3〜1腿 •ガラス繊維 E950i), base polymer with melting point 335 ° C, viscosity 30 Pa · s (measured at 350 ° C, shear rate lOOOOZs), pellet dimensions: about 5-3 thighs X about 3-2 marauders X 3 to 1 thigh • glass fiber
( 1) 実施例 1〜 5、 比較例 1〜 8で使用のもの;  (1) Those used in Examples 1 to 5 and Comparative Examples 1 to 8;
旭ファイバ一ガラス (株) 製 CS03JA419 (繊維径 のチョップドストラン ドフアイパー)  Asahi Fiber Glass Co., Ltd. CS03JA419 (fiber diameter chopped strand fiber)
(2) 比較例 9で使用のもの;  (2) used in Comparative Example 9;
日東紡 (株) 製 PF70 (繊維径 ΙΟ ΠΚ 繊維長 8θ ΐηミルドファイバー) •滑剤; 日本油脂 (株) 製ユニスター Η- 476  Nittobo PF70 (fiber diameter (ΠΚ fiber length 8θ ΐη milled fiber) • Lubricant; Unistar manufactured by NOF Corporation Η-476
(コンパウンド設備)  (Compound equipment)
,押出機; 日本製鋼所製、 二軸スクリュー押出機 Τ Ε Χ— 3 0 0; (スクリュー径 32腿、 L /D : 38. 5)  , Extruder; twin screw extruder manufactured by Nippon Steel Works Τ Ε Χ—300; (screw diameter 32 thigh, L / D: 38.5)
押出機のスクリユー概略を図 3に示す。  Fig. 3 shows the outline of the screw of the extruder.
メインフィード口 1 1; C 1 Main feed port 1 1; C 1
可塑化部 12 ; C 4〜C 5 (構成:上流側より、順ニーディング、逆ニーディング、 長さ 128腿) Plasticization section 12; C4 to C5 (Composition: from the upstream, forward kneading, reverse kneading, length 128 thighs)
サイドフィード口 13; C 5 Side feed port 13; C 5
混練部 14; C 6〜C 8 (構成:上流側より、順ニーディング、直交ニーディング、 逆二一ディング、 逆フライト、 順ニーディング、 逆ニーディング、 逆フライト、 長さ 352腿) Kneading part 14; C6 to C8 (Construction: from upstream, forward kneading, orthogonal kneading, reverse nipping, reverse flight, forward kneading, reverse kneading, reverse flight, length 352 thighs)
メインフィード口へのフィーダ一; 日本製鋼所製スクリユー式ロスインウェイト フィーダ一 サイドフィード口へのフィーダ一; Feeder to main feed port; Screw-in type loss-in-weight feeder manufactured by Nippon Steel Works Feeder to side feed opening;
ペレツト樹脂; K— T R O N社製スクリュー式ロスインウェイトフィ一ダ一 ガラス繊維; 日本製鋼所製スクリュー式ロスインウェイトフィーダー  Pellet resin; Screw-type loss-in-weight feeder manufactured by K-TRON Corporation Glass fiber; Screw-type loss-in-weight feeder manufactured by Nippon Steel Works
(押出条件)  (Extrusion conditions)
シリンダー温度;メインフィード口 11のシリンダー C 1のみが 200°Cであり、 他 のシリンダ一温度は全て 350°Cとした。 Cylinder temperature: Only cylinder C1 at main feed port 11 was 200 ° C, and all other cylinder temperatures were 350 ° C.
ダイ温度; 350°C Die temperature; 350 ° C
(組成物の混練および押出方法) 。  (Method of kneading and extruding composition).
上記二軸スクリユー押出機を用い、 液晶性ポリマーのペレツトをメインフィー ドロ 11及びサイドフィード口 13から供給し、 滑剤をメインフィード口 11から、 ガラス繊維をサイドフィード口 13から供給した。 サイドフィード口には、 二軸 サイドフィーダ一を用いて供給し、 液晶性ポリマーペレット、 滑剤、 ガラス繊維 の割合は表 1の割合になるように、 重量フィーダ一を用いて制御した。 スクリュ ―回転数及び押出量は表 1のように設定し、ダイ 16からストランド状に吐出させ た溶融樹脂組成物を夕ナカ製作所製メッシュベルトコンベアで搬送しつつ、 スプ レー噴霧^により冷却した後、 カッティングしペレットを得た。 このペレットか ら射出成形機により上記試験片を作製し、.評価したところ、 表 2に示す結果を得 た。  Using the twin-screw extruder described above, a pellet of liquid crystalline polymer was supplied from the main feed port 11 and the side feed port 13, a lubricant was supplied from the main feed port 11, and a glass fiber was supplied from the side feed port 13. The side feed port was supplied using a biaxial side feeder, and the ratio of liquid crystalline polymer pellets, lubricant, and glass fiber was controlled using a weight feeder so as to be as shown in Table 1. Screw-The number of revolutions and the extrusion rate are set as shown in Table 1.After the molten resin composition discharged from the die 16 in the form of a strand is conveyed by a mesh belt conveyor manufactured by Yunaka Manufacturing Co., Ltd., and cooled by spray spray ^ Cutting was performed to obtain pellets. The test pieces were prepared from the pellets using an injection molding machine and evaluated. The results shown in Table 2 were obtained.
尚、 実施例 ·比較例の各複合樹脂組成物におけるガラス繊維の配合量と重量平 均長さとの関係を、 図 1にプロットした。 メインフィード口 11からの添加量 サイドフィード口 13からの添加量 回転数 押出量In addition, the relationship between the blending amount of glass fiber and the weight average length in each of the composite resin compositions of Examples and Comparative Examples was plotted in FIG. Amount added from main feed port 11 Amount added from side feed port 13
(SJ 1%) (重量%) 、rpm) (kg/hr) 液晶性ポリマー 滑剤 wiaS ガラス繊維 (SJ 1%) (wt%), rpm) (kg / hr) Liquid crystalline polymer Lubricant wiaS glass fiber
実施例 1 29.7 0.3 30 40 300 35 実施 2 9.7 0.3 50 40 300 35 実施例 3 14.7 0.3 45 40 300 35 実施例 4 14.7 0.3 40 45 300 25 実施例 5 14.7 0.3 35 50 300 25 比較例 1 9.7 0.3 60 30 300 35 比較例 2 64.7 0.3 ― 35 300 25 比較例 3 64.7 0.3 ― 35 300 25 比較例 4 9.7 0.3 55 35 300 35 比較例 5 59.7 0.3 ― 40 300 25 比較例 6 54.7 0.3 ― 45 300 25 比較例 7 44.7 0.3 5 50 300 25 比較例 8 39.7 0.3 5 55 300 25 比較例 9 59.7 0.3 ― 40 300 25 Example 1 29.7 0.3 30 40 300 35 Example 2 9.7 0.3 50 40 300 35 Example 3 14.7 0.3 45 40 300 35 Example 4 14.7 0.3 40 45 300 25 Example 5 14.7 0.3 35 50 300 25 Comparative example 1 9.7 0.3 60 30 300 35 Comparative Example 2 64.7 0.3 ― 35 300 25 Comparative Example 3 64.7 0.3 ― 35 300 25 Comparative Example 4 9.7 0.3 55 35 300 35 Comparative Example 5 59.7 0.3 ― 40 300 25 Comparative Example 6 54.7 0.3 ― 45 300 25 Comparative Example 7 44.7 0.3 5 50 300 25 Comparative example 8 39.7 0.3 5 55 300 25 Comparative example 9 59.7 0.3 ― 40 300 25
ガラス繊維 ガラス繊維の 溶融粘度 リフロー前 リフロー前後 曲げ弾性率 添加量 重量平均繊維長 の平面度 の平面度の差 (重量%) ( m ) (Pa -s) (mm kmm) (GPa) 実施例 1 40 320 40 0.073 0.009 16.2 実施例 2 40 190 36 0.059 0.003 15.6 実施例 3 40 226 31 0.048 0.002 15.6 実施例 4 45 264 37 0.083 0.009 18.5 実施例 5 50 255 39 0.083 0.007 20.0 比較例 1 30 214 32 0.061 0.045 1.4.0 比較例 2 35 370 57 0.073 0.021 17.8 比較例 3 35 430 59 0.069 0.027 17.9 比較例 4 35 229 32 0.067 0.102 15.8 比較例 5 40 397 56 0.092 0.010 19.4 比較例 6 45 359 60 * * 20.5 比較例 7 50 315 67 * * 20.9 比較例 8 55 305 80 * * 22.0 比較例 9 40 80 57 0.072 0.088 15.5 Glass fiber Melt viscosity of glass fiber Before reflow Before and after reflow Flexural modulus Addition Difference in flatness of weight average fiber length Flatness of flatness (% by weight) (m) (Pa-s) (mm kmm) (GPa) Example 1 40 320 40 0.073 0.009 16.2 Example 2 40 190 36 0.059 0.003 15.6 Example 3 40 226 31 0.048 0.002 15.6 Example 4 45 264 37 0.083 0.009 18.5 Example 5 50 255 39 0.083 0.007 20.0 Comparative example 1 30 214 32 0.061 0.045 1.4.0 Comparative Example 2 35 370 57 0.073 0.021 17.8 Comparative Example 3 35 430 59 0.069 0.027 17.9 Comparative Example 4 35 229 32 0.067 0.102 15.8 Comparative Example 5 40 397 56 0.092 0.010 19.4 Comparative Example 6 45 359 60 * * 20.5 Comparative Example 7 50 315 67 * * 20.9 Comparative Example 8 55 305 80 * * 22.0 Comparative Example 9 40 80 57 0.072 0.088 15.5
*流動性が悪いために未充填の成形品しか得られなかった。 * Due to poor fluidity, only unfilled molded products were obtained.

Claims

請求の範囲 The scope of the claims
1. (A) 液晶性ポリマーに (B) 繊維状充填剤を配合した (C) 複合樹脂組成物 (但 し、 配合する(B) 繊維状充填剤の配合量と重量平均長さとの関係が、 以下の領域 (D) の規定内を満足するもの) 力 形成される、 外枠の内部に格子構造を有する 平面状コネクター。 1. (A) A liquid crystalline polymer mixed with (B) a fibrous filler (C) A composite resin composition (however, (B) The relationship between the amount of the fibrous filler and the weight average length is A) A flat connector having a lattice structure inside the outer frame formed therein.
[領域 (D)]  [Area (D)]
X軸を (B) 繊維状充填剤の配合量 ((C) 複合樹脂組成物中の重量%) 、 Y軸を (B)繊維状充填剤の重量平均長さ ( m) として、 以下の(1) 〜 ) の関数で囲まれる領域  Assuming that the X axis is (B) the amount of the fibrous filler ((C)% by weight in the composite resin composition) and the Y axis is (B) the weight average length (m) of the fibrous filler, the following ( 1) The area enclosed by the functions of ~)
(1) X=36  (1) X = 36
(2) X=53  (2) X = 53
(3) Y = 160  (3) Y = 160
(4) Υ=360  (4) Υ = 360
(5) Υ= (18222/Χ) -84.44  (5) Υ = (18222 / Χ) -84.44
2. コネクターが、 格子部のピッチ間隔が 2廳以下、 格子部の厚みが 0.5匪以 下、製品全体の高さが 5.0匪以下のものである請求項 1記載の平面状コネクター。2. The flat connector according to claim 1, wherein the connector has a grid portion having a pitch interval of 2 or less, a grid portion having a thickness of 0.5 or less, and a total product height of 5.0 or less.
3. (C) 複合樹脂組成物が、 L=20腿、 d=l匪のキヤビラリ一式レオメータ を使用し、 温度 360° (:、 剪断速度 1000Z sで I S〇 1 1443に準拠して測定し た見掛け溶融粘度が 55P a · s以下のものである請求項 1又は 2記載の平面状コ ネクター。 3. (C) The composite resin composition was measured in accordance with IS〇1443 at a temperature of 360 ° (:, shear rate 1000Z s) using a capillaries set rheometer of L = 20 thighs, d = l 3. The planar connector according to claim 1, wherein the apparent melt viscosity is 55 Pa · s or less.
4. ピーク温度 230〜280°Cで表面実装のための I Rリフロー工程を経る前の平 面度が 0.09腿以下であり、 なおかつリフロー前後の平面度の差が 0.02mm以下で ある請求項 1または 2項記載の平面状コネクター。 4. The flatness before going through the IR reflow process for surface mounting at a peak temperature of 230 to 280 ° C is 0.09 thigh or less, and the difference in flatness before and after reflow is 0.02 mm or less. The planar connector according to item 2.
5 . (C) 複合樹脂組成物が、 L =20腦、. d = 1醒のキヤピラリー式レオメータ を使用し、 温度 360 、 剪断速度 1000/ sで I S O 1 1 4 4 3に準拠して測定し た見掛け溶融粘度が 55 P a · s以下のものであり、 ピーク温度 230〜280 で表面 実装のための I Rリフロー工程を経る前の平面度が 0. 09nun以下であり、なおかつ リフロー前後の平面度の差が 0. 02mm以下である請求項 1または 2項記載の平面 状コネクタ一。 5. (C) The composite resin composition was measured using a capillary rheometer with L = 20 and d = 1 at a temperature of 360 and a shear rate of 1000 / s in accordance with ISO 11443. The apparent melt viscosity is 55 Pas or less, the flatness before going through the IR reflow process for surface mounting at a peak temperature of 230 to 280 is 0.09 nun or less, and the flatness before and after reflow. 3. The flat connector according to claim 1, wherein the difference between the two is 0.02 mm or less.
PCT/JP2005/006220 2004-03-26 2005-03-24 Planar connector WO2005093909A1 (en)

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PCT/JP2005/006220 WO2005093909A1 (en) 2004-03-26 2005-03-24 Planar connector

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JP5485216B2 (en) 2011-04-01 2014-05-07 ポリプラスチックス株式会社 Planar connector
US9353263B2 (en) * 2011-11-15 2016-05-31 Ticona Llc Fine pitch electrical connector and a thermoplastic composition for use therein
JP5753143B2 (en) 2012-09-21 2015-07-22 ポリプラスチックス株式会社 Totally aromatic polyester and polyester resin composition, and polyester molded article
JP5753144B2 (en) 2012-09-21 2015-07-22 ポリプラスチックス株式会社 Totally aromatic polyester and polyester resin composition, and polyester molded article
JP5826404B2 (en) 2012-09-27 2015-12-02 ポリプラスチックス株式会社 Composite resin composition and planar connector molded from the composite resin composition
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CN1934756A (en) 2007-03-21
TWI343676B (en) 2011-06-11
TW200537757A (en) 2005-11-16
CN100539317C (en) 2009-09-09
JP2005276758A (en) 2005-10-06
JP4717366B2 (en) 2011-07-06

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